ES2897479T3 - Process for preparing a dental composite resin material and product prepared using the dental composite resin material - Google Patents

Abstract

Process for preparing a dental composite resin material, characterized in that it comprises: (1) weighing each of the raw materials, including an ethylenically unsaturated monomer, a reinforcing fiber, a filler, an initiator, a polymerization inhibitor and a colorant; wherein the ratio of total weight of reinforcing fiber and filler to weight of ethylenically unsaturated monomer is 90:10-10:90, preferably 85:15-65:35; the initiator is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the polymerization inhibitor is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the colorant is 0.001-0.2%, preferably 0.005-0.1% by weight relative to the total weight of the ethylenically unsaturated monomer; the reinforcing fiber and the load; and the weight ratio of filler to reinforcing fiber is 10:90-55:45. (2) mixing the heavy raw materials except the reinforcing fiber to obtain a composite resin monomer precursor; (3): Impregnate the heavy reinforcing fiber in the composite resin monomer precursor for 1-5 hours, preferably 2-3 hours, at a negative impregnation pressure of less than or equal to 0.1 MPa, obtaining a reinforcing fiber immersed in the composite resin monomer precursor; and (4): subjecting the reinforcing fiber immersed in the composite resin monomer precursor to a solidification treatment, obtaining a dental composite resin material, in which the solidification temperature is 100-200 ºC, preferably , 120-160 °C, the solidification time is 0.5-3 hours, preferably 1.5-2 hours, and the solidification pressure is 10-200 MPa, preferably 10-100 MPa and more preferably 20-60 MPa.

Description

DESCRIPTION

Process for preparing a dental composite resin material and product prepared using the dental composite resin material

technical sector

The present application relates to the field of dental restorations and, in particular, relates to a process for preparing a dental composite resin material and articles prepared therefrom.

State of the prior art

Computer Aided Design and Computer Aided Manufacture (CAD/CAM) technologies were first introduced to the design and fabrication of fixed oral restorations in the early 1970s by Professor Francois Duret from France. These technologies brought a great technological revolution in the dental restoration sector. In them, CAD means using the computer as the main technology to create and apply various digital and graphic information for the designation of articles; and CAM means an automatic manufacturing technology for machining articles through computer controlled machining equipment, such as a CNC (computer numerical control) milling machine. Currently, CAD/CAM systems can successfully fabricate fixed restorations, such as fillings, veneers, crowns, fixed bridges, etc... However, patients have to go to the hospital at least 2-3 times to end the therapeutic process completely. Such frequent and complex subsequent visits entail great inconvenience for patients. With the development of computer technology, a new technology emerges, chair-side digital restoration technology (CAD/CAM chair-side) that can treat patients quickly.

In the chair-side CAD/CAM system, a computer-aided design and computer-aided manufacturing device is placed next to the dental chair. After tooth preparation and the like, the patient's tooth model can be obtained by digital technology, and then the data can be analyzed by computer, and a dental prosthesis (restoration) can be immediately designed and fabricated. The patient will take around 30 minutes to complete the treatment completely, without subsequent complex visits. With chair-side CAD/CAM technology, temporary restoration can be prohibited, restoration fabrication can be completed in a single step, thus saving the patient time and significantly improving the quality of the restoration. Through digital model tracking, restoration design and dental restoration fabrication, higher precision and accuracy can be achieved, thereby improving the success rate of treatment. Problems caused by conventional PFM (porcelain fused to metal) dentures and removable dentures, such as gingiva discoloration and poor marginal fit, can be greatly reduced, and patient satisfaction with treatment can be significantly improved. significant way.

The development of CAD/CAM “chair-side” also drives the development of dental material. Currently, three types of chair-side CAD/CAM dental materials have been developed: machinable ceramic, composite material, and metal. Machinable ceramics include glass-ceramics, glass-infiltrated hybrid ceramics, alumina, zirconia, and the like. The composite material includes resin composite material, resin-infiltrated porous ceramic hybrid material, poly(ether-ether-ketone) (PEEK) material, and the like. The metal is dental titanium and the like.

Among the three materials mentioned above, the resin composite material is an ideal candidate for dental chair-side CAD/CAM due to its good hardness, machinability, abrasion resistance, X-ray resistance and ease of polishing. . In addition, the aesthetic effect of it is similar to that of the natural tooth. However, the strength of CAD/CAM resin composite material is too low with maximum flexural strength around 240 MPa, which can be applied for non-weight-bearing restorations such as fillings, inlays, veneers, simple crowns. CAD/CAM resin composite material cannot be used for supporting dental restorations such as bridges, molars and the like.

Patent CN 101 244 013 discloses a dental composite resin material comprising ethylenically unsaturated monomers, inorganic fillers, optional organic fillers, initiators, reducing agents and polymerization inhibitors, and a process for preparing the dental composite resin material.

Characteristics of the invention

The examples of the present application disclose a method for preparing a dental composite resin material and articles prepared therefrom in order to address the problem of low strength of CAD/CAM composite resin material. The technical solutions are as follows.

The present application discloses, first, a process for preparing a dental composite resin, according to claims 1-14.

The present application also discloses a dental composite resin material according to attached claim 15.

The dental composite resin material prepared by the method disclosed by the present application has the following advantageous effects:

(1) the dental composite resin material disclosed by the present application has extremely high mechanical strength and the flexural strength through experimental determination is up to above 600 MPa, so that the resin material dental composite can be used to fabricate a dental restoration for weight-bearing parts, such as a dental bridge, a weight-bearing dental crown, full dentures, the scaffold for restoring implants and the like;

(2) the dental composite resin material disclosed by the present application has no detectable ethylenically unsaturated monomer residue (no cell toxicity) and therefore has very good biosafety; and

(3) The dental composite resin material disclosed by the present application has a transparency similar to that of a natural tooth, and the light transmittance may be up to above 40%, preferably up to above 55%, so that the dental composite resin material can be used for the fabrication of complete dentures.

Detailed description of the invention

The present application discloses a process for preparing a dental composite resin material, comprising the following steps.

Step (1): Weigh each of the raw materials, including the ethylenically unsaturated monomer, the reinforcing fiber, the filler, the initiator, the polymerization inhibitor and the colorant; wherein the ratio of total weight of reinforcing fiber and filler to weight of ethylenically unsaturated monomer is 90:10-10:90, preferably 85:15-65:35; the initiator is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the polymerization inhibitor is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the colorant is 0.001-0.2%, preferably 0.005-0.1% by weight relative to the total weight of the ethylenically unsaturated monomer; the reinforcing fiber and the load; and the weight ratio of filler to reinforcing fiber is 10:90-55:45.

In a particular embodiment of the present application, the ethylenically unsaturated monomer includes one of (methyl) acrylate, hydroxyl and epoxy functionalized (methyl) acrylate, or a combination thereof and, preferably, includes one of bisphenol A-methacrylate (Bis-GMA), bisphenol A-ethoxylated dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate ( ^t E ^g DMA), hydroxyethyl methacrylate (HEMA), poly(ethylene glycol) dimethacrylate ( PEGDMA) and bisphenol A epoxy resin (E-44 epoxy resin), or a combination thereof.

In a particular embodiment of the present application, the reinforcing fiber includes one of carbon fiber, glass fiber, quartz fiber, siliceous fiber, ceramic fiber and polymer fiber, or a combination thereof. The reinforcing fiber can be a fiber bundle, a fiber fabric or a fiber batt. The diameter of a single fiber of the reinforcing fiber is in the range of 0.1-25 µm, preferably 0.5-10 µm; and the refractive index of the reinforcing fiber is in the range of 1.40-1.70, preferably 1.45-1.60.

In a particular embodiment of the present application, the load includes the type I load and the type II load. Type I filler is a filler with a particle size in the range of 0.01-10 µm, preferably 0.01-5 µm and more preferably 0.01-1 µm. |om The type I filler may be inorganic fillers or prepolymerized organic fillers that are insoluble in the composite resin monomer precursor, or a combination of both. Type I filler includes, but is not limited to, at least one of quartz, barium glass, lanthanum glass, borosilicate glass, silicon oxide-zirconium oxide composite powder, silicon oxide composite powder -ytterbium oxide, polycarbonate filled or not filled with inorganic material, polyepoxide powder and polymerized methacrylic resin.

The refractive index of the type I filler is in the range of 1.48-1.60, preferably 1.50-1.58. Type II filler is a filler with a particle size in the range of 10-100nm, preferably 10-70nm and more preferably 15-50nm. The type II filler preferably includes at least one of silicon oxide nanopowder and zirconium oxide nanopowder, and the weight ratio of type I filler to type II filler is 3 :1-1:1.

The ethylenically unsaturated monomer, reinforcing fiber and filler used in the present application have a refractive index close to each other, so that the appearance of the dental composite resin material prepared by the present application can be much more similar to natural tooth. The combination of the reinforcing fiber and the resin material can significantly increase the strength of the resin material, enabling it to meet the requirement of producing weight-bearing restorations such as dental bridges, molars, and the like. Furthermore, the inventors of the present invention surprisingly found that the addition of the filler could increase the polishability and abrasion resistance of the material. In addition, the inventors of the present invention surprisingly found that the use of the type I filler and the type II filler in a mixture can make the dental composite resin material disclosed by the present application have beneficial effects. of translucency and opalescence similar to those of natural teeth.

In a particular embodiment of the present application, the colorant includes one of red colorant, yellow colorant, and black colorant, or a combination thereof. The red dye is preferably iron oxide red, the yellow dye is selected from iron oxide yellow, bismuth yellow, vanadium-zirconium yellow and cerium-praseodymium yellow, or a combination thereof, and the black colorant is preferably iron oxide black. It can be understood that the amounts of various colorants and the ratio between them can be adjusted according to the actual requirement so as to allow the color of the material to be close to the natural color of the tooth.

In a particular embodiment of the present application, the initiator can be selected from one of dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, t-butyl peroxyacetate and t-butyl peroxybenzoate, or a combination thereof. The polymerization inhibitor can be 2,6-di-t-butyl-p-cresol, of course, other polymerization initiators and inhibitors can also be used. Preferably, the raw materials may also include an accelerator, the accelerator being 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of ethylenically unsaturated monomer ; and the amine accelerator may be N,N-dihydroxyethyl-4-methylaniline.

In a particular embodiment of the present application, the raw materials may further include various additives that are applicable to oral conditions, including, but not limited to, at least one of fluorescent agent, indicator, viscosity modifier, wetting agent, antioxidant, stabilizer and diluent. Step (2): Mix the heavy raw materials except the reinforcing fiber, obtaining a composite resin monomer precursor.

During the specific implementation process, the raw materials except the reinforcing fiber can be dispersed and mixed homogeneously by mechanical stirring or ultrasonic oscillation.

Step (3): impregnate the heavy reinforcing fiber in the composite resin monomer precursor for 1-5 hours, preferably 2-3 hours, at a negative impregnation pressure less than or equal to 0.1 MPa, obtaining a reinforcing fiber immersed in the composite resin monomer precursor.

In a particular embodiment of the present application, in order to increase the bond strength between the reinforcing fiber and the resin, the reinforcing fiber may be subjected to a pretreatment before being impregnated in the composite resin monomer precursor. Pretreatment includes cleaning and surface modification.

Therein, methods for cleaning include, but are not limited to, heat treatment method, solvent impregnation method, or acid/base etching method. The heat treatment method means high temperature calcination, for example, calcination at 400°C for 1 hour. The solvent impregnation method means impregnation with an organic solvent, such as acetone, for 5 hours. Acid/base corrosion method means impregnation with a hydrochloric acid solution or a sodium hydroxide solution at a certain concentration for a period of time, for example, 0.5 hours. It should be noted that different cleaning procedures could be used depending on the reinforcing fiber materials. For example, the acid/base corrosion process can be used for glass fiber, the high-temperature calcination process can be used for siliceous fiber, and the solvent impregnation process can be used for polymer fiber.

Furthermore, the reinforcing fiber can be subjected to surface modification after cleaning. Methods for surface modification include, but are not limited to, coupling agent modification, plasma surface modification, or chemical grafting, or the like. All the mentioned methods for surface modification belong to the prior art and the methods for carrying out the aforementioned surface modification can be obtained by the person skilled in the art, and they will not be particularly limited here in the present application. For example, the procedure cited in the document (Surface modification of carbon microspheres using a silane coupling agent, Sha Li, Feifei Duan, et al., Functional Material, 2011, No. 1, volume 42, pages 25-28) can be use to modify the surface of the reinforcing fiber by means of a coupling agent. The coupling agent includes y-methacryloxy propyl trimethoxysilane (KH-570), y-mercaptopropyl triethoxysilane (KH-580), y-aminopropyl trimethoxysilane (JH-A111), and the like.

Similarly, in a particular embodiment of the present application, the filler may be subjected to surface modification before being mixed with other raw materials. Methods for surface modification include modification with a coupling agent, plasma surface modification treatment or chemical grafting, or the like. Details can be seen in the reinforcing fiber log.

Step (4): subjecting the reinforcing fiber immersed in the composite resin monomer precursor to a solidification treatment, obtaining a dental composite resin material, in which the solidification temperature is 100-200 °C, so preferably 120-160 °C, the solidification time is 0.5-3 hours, preferably 1.5-2 hours, and the solidification pressure is 10-200 MPa, preferably 10- 100 MPa and more preferably 20-60 MPa. The above solidification treatment under pressure and heating increases the contact area between the ethylenically unsaturated monomer and the initiator, and thus improves the efficiency of the solidification reaction, reduces residues of polymer monomer, improves the biocompatibility of the material of composite resin and effectively increases the strength of the composite resin material. It should be noted that the pressurizing and heating equipment used in the present application is commonly used in the art, as long as it can achieve the objectives of the present application, and will not be particularly limited here in the present application. For example, pressurizing and heating equipment from Shenzhen Chuangjiahong Machinery Co., Ltd. can be used.

The technical solution of the present application will be described with reference to specific examples, below. Example 1

Each of the raw materials is weighed according to the formulation of example 1 in table 1, then the heavy raw materials, except the glass fiber bundles, are mechanically dispersed and mixed, obtaining a monomer precursor of composite resin.

The heavy glass fiber bundles are calcined at a temperature of 400 °C for 1 hour; and after cooling to room temperature, they are subjected to a modification treatment with a coupling agent. Specifically, glass fiber bundles can be soaked in ethanol containing KH570 hydrolyzate (in which the volume ratio of KH570 hydrolyzate to ethanol is 1:3), treated at 65°C for 2 hours and then dry at 100°C for 4 hours.

The dried reinforcing fiber is impregnated in the composite resin monomer precursor for 2 hours, with a negative impregnation pressure of about 0.1 MPa, to obtain a reinforcing fiber immersed in the composite resin monomer precursor. Next, the reinforcing fiber immersed in the composite resin monomer precursor is subjected to a solidification treatment under the conditions of the solidification process of Example 1 in Table 1, obtaining the dental composite resin material.

Examples 2-8

The raw materials and the conditions of the preparation process indicated in table 1 are applied to prepare the dental composite resin material, according to the procedure indicated in example 1. In this sense, in example 2, the glass powder loads lanthanum, silicon nanooxide and zirconium nanooxide are first subjected to coupling agent modification before being mixed with other raw materials. The treatment procedure is the same as for the fiberglass bundles in Example 1. The dental composite resin material prepared in Example 6 has an A2 shade from the VITA 16 shade guide, the dental composite resin material prepared in example 7 has an A3 shade from the VITA 16 shade guide and the dental composite resin material prepared in example 8 has a gingival shade.

Measurement of mechanical behaviors

The flexural strength, flexural modulus, fracture toughness, and light transmittance of the dental composite resin materials prepared in Examples 1-8 and obtained from the commercial Trilor CAD block are measured, respectively. CAM reinforced with fibers from Bioloren Srl, and the results are shown in table 2. In it, the procedure for measuring the flexural strength is according to the standard YY/T 0710-2009/ISO 10477-2004, “Dentistry Polymer -Based Crown and Bridge Materials”. The procedure for measuring the flexural modulus is according to ISO 10477: 2004 Ed.2, “Dentistry Polymer-Based Crown and Bridge Materials”. The procedure for measuring fracture resistance is according to ISO 6872-2008, “Dentistry-Ceramic Materials”, and the procedure for measuring light transmittance is according to JC/T 2020-2010 “Test Method for Transmittance of Translucent Fine Ceramics”.

From table 2 it can be seen that the various behaviors of the composite resin materials dental agents prepared in the examples of the present application are excellent. The increased strength and hardness allow the material to maintain good shape without cracking or fracturing when applied for dental restoration, whether during processing, use or application. Therefore, this material can be widely applied for dental restoration and meet the market demand.

Table 2 Comparison between the behaviors of the dental composite resin materials prepared in examples 1-8 and the product of Trilor________ ________________________________________________________ "'''-Behavior

Flexural Strength Transmittance Modulus of Strength/Bending MPa/GPa acture/MPa-m1/ span/% E x a m p lo ' ' \

541 ± 24

14,25 ± 0,86

7,65 ± 0,27

32,07 Example 1 601 ± 19 18.25 ± 0.38 9.45 ± 0.16 41.56 Example 2 634 ± 18 21.04 ± 0.99 13.77 ± 0.34 55.00 Example 3 603 ± 15 17 .65 ± 0.57 12.87 ± 0.45 47.37 Example 4 617 ± 12 20.45 ± 0.86 13.60 ± 0.14 47.17 Example 5 602 ± 12 19.28 ± 0.74 9.59 ± 0.36 42.48 Example 6 608 ± 10 18.17 ± 0.65 12.59 ± 0.24 47.43 Example 7 612 ± 19 19.36 ± 0.47 13.19 ± 0, 16 48.11 Example 8 605 ± 8 18.29 ± 0.56 12.89 ± 0.37 46.26 Trilor

541 ± 24

14.25 ± 0.86

7.65 ± 0.27

32.07

Biocompatibility Measurement

With a higher degree of solidification, the composite resin material has less residual polymer monomer; so, the water absorption, solubility and chemical solubility of the materials are less, and the biocompatibility of the materials is better. The water absorption, solubility and chemical solubility of the dental composite resin material prepared in Example 1 and the commercial fiber-reinforced Trilor CAD/CAM block of Bioloren Srl are measured, respectively, and the results are indicated in the table 3. Therein, the procedure for measuring water absorption and solubility is according to YY/T0710-2009/ISO 10477-2004, "Dentistry Polymer-Based Crown and Bridge Materials", and the procedure for measuring solubility chemistry is according to ISO 6872-2008, ' Dentistry-Ceramic Material'.

Tl. m r i n nr l m r mi n l m l 1 l r Tril r

From Table 3 it can be seen that the dental composite resin material prepared in Example 1 has lower water absorption, solubility and chemical solubility compared to Trilor from Bioloren, indicating that the preparation method of the present application is beneficial to decrease polymer monomer residues, thus improving the biocompatibility and biosafety of dental composite resin material.

The process for preparing a dental composite resin material and articles prepared therefrom disclosed by the present application have been described in detail above. The theory and embodiments of the present application are illustrated with reference to specific examples herein. The above descriptions of the examples are only intended to be helpful in understanding the process and main concept of the present application.

Claims (15)

1. Procedure for preparing a dental composite resin material, characterized in that it comprises: (1) Weighing each of the raw materials, including an ethylenically unsaturated monomer, a reinforcing fiber, a filler, an initiator, a polymerization inhibitor, and a colorant; wherein the ratio of total weight of reinforcing fiber and filler to weight of ethylenically unsaturated monomer is 90:10-10:90, preferably 85:15-65:35; the initiator is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the polymerization inhibitor is 0.05-1%, preferably 0.1-0.3% by weight relative to the weight of the ethylenically unsaturated monomer; the colorant is 0.001-0.2%, preferably 0.005-0.1% by weight relative to the total weight of the ethylenically unsaturated monomer; the reinforcing fiber and the load; and the weight ratio of filler to reinforcing fiber is 10:90-55:45. (2) mixing the heavy raw materials except the reinforcing fiber to obtain a composite resin monomer precursor; (3) : Impregnate the heavy reinforcing fiber in the composite resin monomer precursor for 1-5 hours, preferably 2-3 hours, at a negative impregnation pressure of less than or equal to 0.1 MPa, obtaining a reinforcing fiber immersed in the composite resin monomer precursor; and (4) : subjecting the reinforcing fiber immersed in the composite resin monomer precursor to a solidification treatment, obtaining a dental composite resin material, in which the solidification temperature is 100-200 °C, preferably , 120-160 °C, the solidification time is 0.5-3 hours, preferably 1.5-2 hours, and the solidification pressure is 10-200 MPa, preferably 10-100 MPa and more preferably 20-60 MPa. 2. Process according to claim 1, characterized in that the raw materials also include an accelerator, which is 0.05-1% by weight with respect to the weight of the ethylenically unsaturated monomer. 3. Process, according to claim 2, characterized in that the raw materials also include an accelerator that is 0.1-0.3% by weight with respect to the weight of the ethylenically unsaturated monomer. 4. Process according to claim 2, characterized in that the accelerator is N,N-dihydroxyethyl-4-methylaniline. 5. Procedure, according to claim 1, characterized in that the raw materials also include, at least, one of fluorescent agent, indicator, viscosity modifier, wetting agent, antioxidant, stabilizer and diluent. 6. Process according to claim 1, characterized in that the ethylenically unsaturated monomer includes one of (meth)acrylate, hydroxyl-functionalized (meth)acrylate and epoxy resin or a combination thereof. 7. Process according to claim 6, characterized in that the ethylenically unsaturated monomer includes one of bisphenol A-glycidyl methacrylate, bisphenol A-ethoxylated dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, hydroxyethyl methacrylate, poly(ethylene glycol) dimethacrylate and epoxy resin with bisphenol A, or a combination thereof. 8. Method, according to claim 1, characterized in that the reinforcing fiber includes one of carbon fiber, glass fiber, quartz fiber, siliceous fiber, ceramic fiber and polymer fiber, or a combination thereof; the reinforcing fiber is a fiber bundle, a fiber fabric or a fiber batt; the diameter of a single fiber of the reinforcing fiber is in the range of 0.1-25 pm, preferably 0.5-10 pm; and the refractive index of the reinforcing fiber is in the range of 1.40-1.70, preferably 1.45-1.60. 9. Method according to claim 1, characterized in that the load includes a type I load and a type II load; type I filler is a filler with a particle size in the range of 0.01-10 pm, and is selected from inorganic fillers and/or prepolymerized organic fillers that are insoluble in the composite resin monomer precursor; the refractive index of the type I load is in the range of 1.48-1.60; type II filler has a particle size in the range of 10-100 nm; and the weight ratio of type I filler to type II filler is 3:1-1:1. 10. Method, according to claim 9, characterized in that the type I filler includes, at least, one of quartz, barium glass, lanthanum glass, borosilicate glass, powder composed of silicon oxide-zirconium oxide, powder silicon oxide-ytterbium oxide compound, polycarbonate filled or not filled with inorganic material, polyepoxide powder and polymerized methacrylic resin; the refractive index of the type I load is in the range of 1.50-1.58; type II filler includes at least one of silicon oxide nanopowder and zirconium oxide nanopowder. 11. Method, according to claim 1, characterized in that the load is subjected to surface modification before being mixed with other raw materials, and the surface modification process includes the modification with a coupling agent, modification by plasma surface treatment or modification by chemical grafting. 12. Method according to claim 1, characterized in that the colorant includes one of red colorant, yellow colorant and black colorant, or a combination thereof; the red dye is iron oxide red; the yellow colorant is selected from iron oxide yellow, bismuth yellow, vanadium-zirconium yellow, and cerium-praseodymium yellow, or a combination thereof; and the black colorant is iron oxide black. 13. Process according to claim 1, characterized in that the initiator is selected from dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, t-butyl peroxyacetate and t-butyl peroxybenzoate, or a combination thereof; and the polymerization inhibitor is 2,6-di-t-butyl-p-cresol. 14. Process according to any of claims 1-13, characterized in that the reinforcing fiber is subjected to a pretreatment before impregnation; and the pretreatment comprises cleaning and modifying the surface; wherein methods for cleaning include heat treatment, solvent impregnation method, or acid/base etching method; and methods for surface modification include coupling agent modification, plasma surface treatment modification or chemical grafting modification. 15. Dental composite resin material that can be obtained with the procedure according to any of claims 1-14. REFERENCES CITED IN THE DESCRIPTION This list of references cited by the applicant is solely for the convenience of the reader. They are not part of the European Patent document. Even considering that the compilation of the references has been done with great care, errors or omissions cannot be ruled out; the EPO disclaims any liability in this regard. Patent Documents Cited in Description • CN 101244013 Non-patent literature cited in description • SHA LI ; FEIFEI-DUAN et al. Surface modification of • Dentistry Polymer-Based Crown and Bridge Materials. carbon microspheres using a silane coupling agent. ISO10477:2004 Functional Material, 2011, Vol. 42 (1), 25-28 • Denistry-Ceramic Materials. ISO6872-2008 • Dentistry Polymer-Based Crown and Bridge Materials. • Test Method for Transmittance of Translucent Fine YY/T 0710-2009/ISO 10477-2004 Ceramics. YT/T 2020-2010